CN100416722C - Activated carbon deposited nickel oxide as super capacitor anode material and preparing method - Google Patents

Activated carbon deposited nickel oxide as super capacitor anode material and preparing method Download PDF

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Publication number
CN100416722C
CN100416722C CNB2003101077144A CN200310107714A CN100416722C CN 100416722 C CN100416722 C CN 100416722C CN B2003101077144 A CNB2003101077144 A CN B2003101077144A CN 200310107714 A CN200310107714 A CN 200310107714A CN 100416722 C CN100416722 C CN 100416722C
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China
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active carbon
nickel
deposited
nickel oxide
activated carbon
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CN1545115A (en
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袁国辉
姜兆华
褚德威
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The present invention discloses activated carbon deposited nickel oxide as a super capacitor anode material and a preparing method, which relates to activated carbon on which nickel oxide deposits as an electrochemical super capacitor anode active material and preparing technology thereof. The deposit amount of the nickel oxide deposits on activated carbon is 1.0 to 14.0 mg/g, the activated carbon is impregnated in Ni (NO3) 2 solution with the concentration of 0.1 to 2.0 mol/L, impregnating fluid is oscillated by supersonic waves in the period of impregnation, and filter cakes are dispersed into excessive NaOH solution with the concentration of 1.0 to 2.0 mol/L and impregnated for 3 to 5 hours; an anode piece is coated with paste, vacuum drying is carried out the anode piece under the condition of 110 DEG C, and the anode piece is compacted on a calender so that a finished product of an anode is obtained by paring burs off; the surface area of the anode is controlled from 0.1 to 10 mA/cm<2> by activating current, the potential of charging and discharging is within the range of-0.5 to 0.35V, and the process of activation is repeated for three times. The present invention has the advantages that simple and easy method, reliable quality of products and obviously increased working voltage.

Description

The ultracapacitor positive electrode and the preparation method that constitute by the active carbon of nickel deposited oxide
Technical field
The present invention relates on active carbon the nickel deposited oxide as the preparation technology of electric chemical super capacitor positive electrode active materials.
Background technology
The electric capacity of electric chemical super capacitor mainly is made of two aspects, based on the double layer capacity of the bilayer on electrode/solution interface and the pseudo-capacitance that reacts based on interface two dimension faraday.The former relies on the electrode material with high-specific surface area, and as active carbon, the latter then relies on some transition metal oxide, as RuO 2, NiO xThe advantage that with the active carbon is the electrochemical capacitor of electrode material be more higher than electric capacity, material is easy to get, with low cost, and technology comparative maturity; Shortcoming is that operating voltage is lower, be 1V to the maximum, and energy density is lower.With RuO 2For the advantage of the electrochemical capacitor of electrode material is to have the much higher ratio electric capacity of specific activity charcoal, but, limited its following possible application because price is extremely expensive.
Summary of the invention
The purpose of this invention is to provide a kind of ultracapacitor positive electrode and preparation method who is made of the active carbon of nickel deposited oxide, it is simple that it has method, reliable product quality, the characteristics that capacitor output energy obviously improves.The present invention is made up of active carbon and the nickel oxide that is deposited on the active carbon, and the deposition that is deposited on the nickel oxide on the active carbon is 1.0～14.0mg/g.Method of the present invention is realized by following steps: take by weighing the 3g active carbon with assay balance, put into beaker, with the Ni (NO for preparing in advance 3) 2Concentration is the decorating liquid 30ml ultrasonic immersing 3 hours of 0.2mol/L, then material is filtered by the suction filtration mode.It is in the NaOH solution of 1.0mol/L that the filter cake that obtains is distributed to excessive, concentration, ultrasonic immersing 4 hours.Filter, clean powdered carbon, reach 8 until filtrate pH value.With the raw material of wood-charcoal material oven dry after filtering, bake out temperature is 125 ℃, and the time is 20 hours.Absorbent charcoal material after the modification that obtains.Adopt atom absorption method to record that nickel content is 13.6mg/g in this raw material of wood-charcoal material.Take by weighing 200mg modified activated carbon material, take by weighing the agent of 25mg graphite, the mode by mechanical oscillation fully mixes.Add 7ml distilled water, the 5.5mgCMC aqueous solution, 9mgPTFE emulsion successively.Add on one side, by mechanical agitation make it even on one side, last furnishing viscosity paste.Adopt manual (or mechanical system) to be coated with in the collector of lug in the good and welding of prior sanction above-mentioned cream of becoming reconciled, the chi of collector, in being 20 * 30mm 2, it is even to require to be coated with cream, must not occur that thin and thick differs or the situation of remaining pore.The vacuumize 8 hours under 110 ℃ of temperature of pole piece that cream finishes will be coated with.Pole piece compacting after will drying on the calender (or hydraulic press) obtains the finished product positive pole behind the burr through paring off the edge.Method of the present invention is realized by following steps: (A) nickel deposited oxide on active carbon; Active carbon is immersed in the Ni (NO that concentration is 0.1～2.0mol/L 3) 2In the solution, active carbon and Ni (NO 3) 2The w/v of solution is 1: 5～10, dip time is 3～4 hours, with ultrasonic wave maceration extract is vibrated during the dipping, then maceration extract is filtered out, the filter cake that obtains is distributed among the NaOH or KOH solution that excessive concentration is 1.0～2.0mol/L, flooded 3～5 hours, use supersonic oscillations simultaneously, filter then, cleaning powdered carbon to the pH value of filtrate is that cleaning in 8 o'clock finishes, with the vacuumize 20 hours under 125 ℃ of temperature of raw material of wood-charcoal material, obtaining deposition is the modified activated carbon material of 1.0～14.0mg/g nickel oxide; (B) electrode preparation; Be mixed into cream by following composition: modified activated carbon material 80wt%, electrically conductive graphite 10wt%, carboxymethyl cellulose (CMC) 2.5wt%, ptfe emulsion (PTFE) 4.5wt%, distilled water 3wt%; The modified activated carbon material that takes by weighing and the electrically conductive graphite mode by mechanical oscillation is fully mixed, add distilled water, the CMC aqueous solution, PTFE emulsion successively, make it even while add by mechanical agitation; Collector adopts foaming metal nickel or metal nickel screen, and the electrode lug adopts the metal nickel foil, and lug and collector adopt the spot welding mode to weld; Above-mentioned cream of becoming reconciled is coated with prior sanction well and in the collector of soldering polar ear, it is even that requirement is coated with cream, avoid occurring that thin and thick differs or the situation of remaining pore, can adopt craft or mechanical system to be coated with cream, pole piece vacuumize under 110 ℃ of conditions that cream finishes will be coated with, be 8～10 hours drying time, and the pole piece compacting after will drying on calender or the hydraulic press obtains finished electrode behind the burr through paring off the edge then; (C) electrode activation; The activation electric current for the surface area control range of electrode at 0.1～10mA/cm 2, discharging and recharging current potential between-0.5～0.35V scope, activation process repeats three circulations, and the charging termination current potential is 0.35V.Adopt the electric chemical super capacitor positive pole of common Preparation of Activated Carbon, during as electrolyte, activation back oxygen evolution potential is generally at 0.184V at 6mol/l KOH solution, and when forming capacitor with common activated carbon negative electrode of the same race, operating voltage is no more than 1V usually.And the electrode of employing modified activated carbon material preparation of the present invention, under the situation of the different amount of deposition nickel oxides, oxygen evolution potential all is significantly improved, and can bring up to 0.220～0.290V.If form capacitor with common activated carbon negative electrode, operating voltage will can improve 0.036～0.106V above 1V, increase rate 3.6～10.6%.Because E=0.5CV 2, the capacitor output energy that causes thus will obviously improve.Activation process has important effect for the oxygen evolution potential that improves electrode.The absorbent charcoal material of nickel deposited oxide, oxygen evolution potential only is 0.043V before the activation.After the activation through 3 cycles, oxygen evolution potential surpasses 0.22V, can reach 0.295V.For the electrode of common active carbon composition, oxygen evolution potential is 0.184V before the activation, reaches 0.22V after the activation equally.This result shows before the capacitor fitting tight, an electrode activation process to be arranged.If this process not, the operating voltage of capacitor and energy output will be given a discount.The above-mentioned electrode potential that relates to all is the current potential of the Hgo/Hg reference electrode of 6mol/L KOH with respect to electrolyte.
Embodiment
Embodiment one: present embodiment is made up of active carbon and the nickel oxide that is deposited on the active carbon, and the deposition that is deposited on the nickel oxide on the active carbon is 1.0～14.0mg/g.
Embodiment two: the deposition that present embodiment is deposited on the nickel oxide on the active carbon is 1.0～3.0mg/g.
Embodiment three: the deposition that present embodiment is deposited on the nickel oxide on the active carbon is 3.1～7.0mg/g.
Embodiment four: the deposition that present embodiment is deposited on the nickel oxide on the active carbon is 7.1～10.0mg/g.
Embodiment five: present embodiment is realized by following steps: (A) nickel deposited oxide on active carbon; Active carbon is immersed in the Ni (NO that concentration is 0.1～2.0mol/L 3) 2In the solution, active carbon and Ni (NO 3) 2The w/v of solution is 1: 5～10, dip time is 3～4 hours, with ultrasonic wave maceration extract is vibrated during the dipping, then maceration extract is filtered out, the filter cake that obtains is distributed among the NaOH or KOH solution that excessive concentration is 1.0～2.0mol/L, flooded 3～5 hours, use supersonic oscillations simultaneously, filter then, cleaning powdered carbon to the pH value of filtrate is that cleaning in 8 o'clock finishes, with the vacuumize 20 hours under 125 ℃ of temperature of raw material of wood-charcoal material, obtaining deposition is the modified activated carbon material of 1.0～14.0mg/g nickel oxide; (B) electrode preparation; Be mixed into cream by following composition: modified activated carbon material 80wt%, electrically conductive graphite 10wt%, carboxymethyl cellulose (CMC) 2.5wt%, ptfe emulsion (PTFE) 4.5wt%, distilled water 3wt%; The modified activated carbon material that takes by weighing and the electrically conductive graphite mode by mechanical oscillation is fully mixed, add distilled water, the CMC aqueous solution, PTFE emulsion successively, make it even while add by mechanical agitation; Collector adopts foaming metal nickel or metal nickel screen, and the electrode lug adopts the metal nickel foil, and lug and collector adopt the spot welding mode to weld; Above-mentioned cream of becoming reconciled is coated with prior sanction well and in the collector of soldering polar ear, it is even that requirement is coated with cream, avoid occurring that thin and thick differs or the situation of remaining pore, can adopt craft or mechanical system to be coated with cream, pole piece vacuumize under 110 ℃ of conditions that cream finishes will be coated with, be 8～10 hours drying time, and the pole piece compacting after will drying on calender or the hydraulic press obtains finished electrode behind the burr through paring off the edge then; (C) electrode activation; The activation electric current for the surface area control range of electrode at 0.1～10mA/cm 2, discharging and recharging current potential between-0.5～0.35V scope, activation process repeats three circulations, and the charging termination current potential is 0.35V.
Embodiment six: present embodiment is realized by following steps: take by weighing the 3g active carbon with assay balance, put into beaker, with the Ni (NO for preparing in advance 3) 2Concentration is the decorating liquid 30ml ultrasonic immersing 3 hours of 0.2mol/L, then material is filtered by the suction filtration mode.It is in the NaOH solution of 1.0mol/L that the filter cake that obtains is distributed to excessive, concentration, ultrasonic immersing 4 hours.Filter, clean powdered carbon, reach 8 until filtrate pH value.With the raw material of wood-charcoal material oven dry after filtering, bake out temperature is 125 ℃, and the time is 20 hours.Absorbent charcoal material after the modification that obtains.Adopt atom absorption method to record that nickel content is 13.6mg/g in this raw material of wood-charcoal material.Take by weighing 200mg modified activated carbon material, take by weighing the agent of 25mg graphite, the mode by mechanical oscillation fully mixes.Add 7ml distilled water, the 5.5mgCMC aqueous solution, 9mgPTFE emulsion successively.Add on one side, by mechanical agitation make it even on one side, last furnishing viscosity paste.Adopt manual (or mechanical system) to be coated with in the collector of lug in the good and welding of prior sanction above-mentioned cream of becoming reconciled, collector is of a size of 20 * 30mm 2, it is even to require to be coated with cream, must not occur that thin and thick differs or the situation of remaining pore.The vacuumize 8 hours under 110 ℃ of temperature of pole piece that cream finishes will be coated with.Pole piece compacting after will drying on the calender (or hydraulic press) obtains the finished product positive pole behind the burr through paring off the edge.

Claims (5)

1. the ultracapacitor positive electrode that is made of the active carbon of nickel deposited oxide is characterized in that it is made up of active carbon and the nickel oxide that is deposited on the active carbon, and the deposition that is deposited on the nickel oxide on the active carbon is 1.0～14.0mg/g.
2. the ultracapacitor positive electrode that is made of the active carbon of nickel deposited oxide according to claim 1, the deposition that it is characterized in that being deposited on the nickel oxide on the active carbon is 1.0～3.0mg/g.
3. the ultracapacitor positive electrode that is made of the active carbon of nickel deposited oxide according to claim 1, the deposition that it is characterized in that being deposited on the nickel oxide on the active carbon is 3.1～7.0mg/g.
4. the ultracapacitor positive electrode that is made of the active carbon of nickel deposited oxide according to claim 1, the deposition that it is characterized in that being deposited on the nickel oxide on the active carbon is 7.1～10.0mg/g.
5. the preparation method of the ultracapacitor positive electrode that is made of the active carbon of nickel deposited oxide is characterized in that it is realized by following steps: take by weighing the 3g active carbon with assay balance, put into beaker, with the Ni (NO for preparing in advance 3) 2Concentration is the decorating liquid 30ml ultrasonic immersing 3 hours of 0.2mol/L, then material is filtered by the suction filtration mode; It is in the NaOH solution of 1.0mol/L that the filter cake that obtains is distributed to excessive, concentration, ultrasonic immersing 4 hours; Filter, clean powdered carbon, reach 8 until filtrate pH value, with the raw material of wood-charcoal material oven dry after filtering, bake out temperature is 125 ℃, time is 20 hours, absorbent charcoal material after the modification that obtains, adopt atom absorption method to record that nickel content is 13.6mg/g in this raw material of wood-charcoal material, take by weighing 200mg modified activated carbon material, take by weighing the agent of 25mg graphite, mode by mechanical oscillation fully mixes, and adds 7ml distilled water successively, 5.5mgCMC the aqueous solution, the 9mgPTFE emulsion, add on one side, make it even by mechanical agitation on one side, last furnishing viscosity paste adopts craft or mechanical system to be coated with in the collector of lug in the good and welding of prior sanction above-mentioned cream of becoming reconciled, and collector is of a size of 20 * 30mm 2, it is even to require to be coated with cream, must not occur that thin and thick differs or the situation of remaining pore, will be coated with the vacuumize 8 hours under 110 ℃ of temperature of pole piece that cream finishes, and the pole piece compacting after will drying on the calender obtains the finished product positive pole behind the burr through paring off the edge.
CNB2003101077144A 2003-11-20 2003-11-20 Activated carbon deposited nickel oxide as super capacitor anode material and preparing method Expired - Fee Related CN100416722C (en)

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CN101950673A (en) * 2010-07-29 2011-01-19 南京双登科技发展研究院有限公司 High-multiplying-power super capacitor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019461A1 (en) * 1998-09-28 2000-04-06 Hyperion Catalysis International, Inc. Fibril composite electrode for electrochemical capacitors
CN1388540A (en) * 2002-07-12 2003-01-01 四川工业学院 Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000019461A1 (en) * 1998-09-28 2000-04-06 Hyperion Catalysis International, Inc. Fibril composite electrode for electrochemical capacitors
CN1388540A (en) * 2002-07-12 2003-01-01 四川工业学院 Superhigh-capacitance capacitor with composite carbon nanotube and its manufacture

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